Detergent composition



Patented Aug. 25, 1942 2,294,075 DETERGENT COMPOSITION Robert B. Colgate, Huntington, N. Y., and Emil E. Dreger, Summit, N. J., assignors to Colgate- Palmolive-Peet Company, Jersey City, N. J., a corporation of Delaware No Drawing.

Application October 21, 1938, Serial No. 236,352

Claims. (01. 252-121) This invention relates to the art of washing, cleansing and deterging, and more particularly to new compositions useful for such purposes.

Soap has long been used for cleansing various materials in washing operations, and in soft water it is very efficient agent for that purpose; however, natural water is seldom free from active mineral salts, that is, it contains salts which decompose water-soluble soaps and cause the formation of water-insoluble soaps, thus giving rise to curds or scum; consequently, the use of soap in many natural waters has many drawbacks.

The insoluble soapsformed by the use of ordinary soaps in hard water, generally termedcurds or scum, not only reduce the efficiency of the soap by necessitating a greater amount for an efficient washing concentration, but also contribute to undesirable results by their presence. They are frequently formed within the interstices of cloth, thereby making removal extremely difficult if not impossible by the usual washing means. After the cloth is dry, these water-insoluble soaps may become rancid and in that manner impart an unpleasant odor to the material. Also, they modify the shade of the material by contributing a grayish or yellowish cast thereto.

Another way in which insoluble soaps are deposited on materials during the washing operation is this: When the materials are removed from the washing water, a considerable amount of soluble soaps will remain in the fabric or adsorbed thereon. It is the object of rinsing operations to .remove these soluble soaps, but if the rinsing water is hard, insoluble soaps will be formed and remain in the garments. Moreover, where insoluble soaps form a scum on washing or rinsing water, some of this scum will be removed with'the clothes as they are taken from the water. Subsequent wringing serves to force such undesirable compounds more securely into the fabric and insure their retention.

Such undesirable consequences have prompted considerable study and research with the object of retaining the good characteristics and economy of ordinary soaps but the elimination of the bad. Numerous substances have been proposed for admixture with soap to improve its usefulness in hard water, and in some cases improvements have been noted, but other properin that the quantity of lather obtainable from a mixture of the two, containing any substantial proportion of both, is less than that obtainable under the same conditions from the same quantity of either alone. Hence, until now applicants know of no method known to the public which eliminates or frees soap of the shortcomings mentioned.

It is an object of the present invention to provide a washing or detergent composition which gives none of the undesirable effects of soap in hard water and retains the valuable characteristics thereof.

It is another object to provide a composition which will favorably compare in price with that of soap and which produces little or no scum or curd in hard water. It is still a further object to provide a detergent composition which is very soluble in water and has remarkable efliciency in both hard and soft water.

Other objects will become apparent as the disclosures are more fully understood.

Applicants have discovered that a washing and deterging composition having unusually high efficiency in hard water but possessing substantially none of the drawbacks met with in soap ties harmful to an effective and economical washing compound have exhibited themselves. One

of mineral oil sulphonic acids; however, these of the combinations suggested was soap and salts alone may be prepared by mixing soap, sulphonated organic compounds, and water-soluble salts of acids of phosphorus. These mixtures produce little or no curd when dissolved in hard water and show a high efficiency in washing operations conducted in hard water. Inasmuch as substantially no scum or curd is formed, any possibility of unpleasant odors due to rancidity or oxidation of insoluble soaps is precluded in clothes washed in solutions of the new compositions, and no grayish cast is imparted to clothes, such as is sometimes observed when the clothes have been repeatedly washed in solutions containing soap alone. White goods retain their whiteness without the use of bleaches when this composition is used, and no grayish cast is observed as when they are washed with soap alone in hard water. The penetrating and washing powers of the mixture appear to be higher than that of soap alone, .due, it is presumed, to the great solubility, emulsifying power, and marked surface-tension reducing ability of the organic sulphonates, as well as to their adsorptive powers.

Applications have also noted that clothes may be freely washed in water rich in iron compounds without danger of the common iron staining'if the compositions of this invention areemployd. It is believed the iron ions are sequesteredffb'y the compounds in the composition ingsu'ch a way that no insoluble iron compounds possessing the characteristic color of iron compounds are formed and deposited on the fabrics; however, this hypothesis is theory only and the disclosures are not limited thereby. The result is definite even if the theory is not the correct one.

Organic sulphonates in general which function as detergents, such as sulphonates obtained from mineral oils, coal tar distillates, alkyl aromatic compounds, petroleum distillation products, polymerized products, etc., which are water-soluble, or mixtures thereof, are suitable in this invention, but we have found that sulphonates particularly desirable for use in our invention may be made by sulphonating mineral oil extracts obtained by the use of a preferential solvent, said extracts being sulphonated while dissolved in liquid sulphur dioxide. Such sulphonation products may be employed in the form of any of their water-soluble salts, as the sodium, potassium, ammonium, ethanolamine (mono-, di-, or tri-), amine, etc.

Ordinary soaps, as used herein, include sodium, potassium, ammonium, amine, etc., salts of higher fatty acids such as are obtained from cocoanut oil, palm oil, olive oil, tallow, cottonseed oil, etc., and mixtures thereof.

While any of the water-soluble salts of acids of phosphorus function in this invention as an essential component of the composition, the salts of pyrophosphoric, tetraphosphoric, and metaphosphoric acids are preferred. The sodium salts of phosphoric acids are especially desirable in this invention, more specifically sodium pyrophosphate and sodium metaphosphate. A single salt of a particular phosphoric acid may be em ployed or a mixture of salts of a particular phosphoric acid or the salts of a mixture of phosphoric acids may be used. By varying the cation of the phosphoric acids or by utilizing different phosphates in varying proportions, corresponding results may be obtained.

Applicants have found that these phosphorus compounds contribute more than their additive properties to the .letergent mixture; they function as harmonizing agents to render the sulphonate and soap compatible. A mixture of sulphonate and soap only in any material proportions exhibits a reduced lathering or sudsing ability as compared with the same quantity of either component alone; however, when a phosphorus compound is added to such a mixture, the lathering or sudsing ability markedly increases. Furthermore, the efliciency of the mixture containing a phosphate is greater in hard water than without the phosphate, and the avoidance of scum in the rinses appears not to be possible by varying the proportions of soap and sulphonate alone without the addition of the phosphorus compound.

The sulphonate found most desirable in the invention may be produced according to the methods disclosed in United States Patents Nos.

2,149,661 and 2,149,662 issued March 7, 1939, to ,Bobert L. Brandt, and application Serial No. ,211,946 filed June 4, 1938, in the name of Robert L. Brandt as inventor.

According to the disclosure of Patent No. 2,149,661, petroleum distillates are extracted with a selective solvent such as liquid sulphur dioxide, that part of petroleum which is soluble in liquid sulphur dioxide being separated with the liquid sulphur dioxide from the insoluble part. The extract is sulphonated while dissolved in the solvent, liquid sulphur dioxide. The acids formed in the sulphonation process are neutralized with sodium hydroxide, ammonum hydroxide or any other base to give a sulphonate as desired.

The method disclosed in Patent No. 2,149,662, represents a refinement in the process of the first filed application in that the petroleum is fractionated to yield a particular cut before extraction, or the extract obtained with liquid sulphur dioxide is thereafter fractionated. In either case, sulphonation is carried out while the fraction or extract is dissolved in liquid sulphur dioxide.

Application Serial No. 211,946, filed June 4, 1938, now Patent No. 2,179,174 issued November 7, 1939, discloses an improvement in the processes described in the earlier applications whereby the color, efllciency, etc., of the particular compounds or detergents previously produced by this inventor are materially enhanced. This improved process represents an economical advance over the previous processes.

In developing and testing this detergent composition, applicants have followed a procedure for measuring the detersive efliciency of such agents, and at the same time their tendency to form scum in washing operations. With the avoidance of scum in the rinses, the deposition of objectionable insoluble substances upon the articles being washed is prevented. In addition, such detergent compositions unquestionably promote greater efficiency in the cleansing operation. These tests for scum were in addition to those to determine the washing efficiency of the various mixtures.

The tables given below indicate the advantages derivable by this invention by comparing the efficiency of two compositions of this invention with two soaps, one pure and one containing alkaline builders, both in relatively soft water and in hard water.

With the efiiciency of soap under the conditions noted arbitrarily taken as a standard of 100, the following comparative values were found:

Detersive efficiency (units of soil removed) [Hardness of water, 50 p. p. m. Concentration of washing agents=0.15%]

Soap Soap (containing builders) as used in Examples II, III, and VII(b) 100 Composition of Example II 100 Composition of Example III 100 With the efiiciency of soap under the conditions noted arbitrarily taken as a standard of 100, the following comparative values were found:

Detersive eflicz'ency (units of soil removed) [Hardness of water, 300 p. p. m.3OC99I]1centration of washing agcnts=0.

Soap 10o Soap (containing builders) as used in Examples II, III, and VII(b) 100 Composition of Example II 250 Composition of Example III 250 total. The most desirable compositions contain about 40 to about 60 per cent soap, about 40 to about per cent of organic sulphonate and about to about 40 per cent of the phosphorus compound. When these proportions are exceeded by only a slight amount, the change in properties of the composition will also be only slight; however, if the proportional limits are materially exceeded, the detergent resulting will be found to compare unfavorably with one prepared according to these disclosures. Within the proportion ranges given above, the following examples (except Example IV) indicate the most desirable compositions.

In some of the compositions as illustrated by the examples, alkaline substances of the class known as alkaline soap builders are found desirable; such compounds include sodium carbonate, sodium silicate, trisodium phosphate, etc. These substances may be included to advantage, provided the proportion thereof neither materialiy affects the proportions of the three essential ingredients nor promotes the formation of scum. I

The examples following are illustrative and not limitative. In every example the same procedure was followed-a ten-minute washing operation followed by two five-minute rinses. The hardness of the water in every case in washes and rinses was 300 p. p. m. as calcium carbonate.

Example I A number of towels were washed in'a washing machine in which a composition of this invention was dissolved to a 0.55% concentration.

The detergent mixture consisted of:

Per cent Tallow soap (Na salt) 50 Organic sulphonate (Na salt) made by the process disclosed in Brandt U. S. Patent No. 2,149,662 20 Sodium pyrophosphate 20 Good detersive action was obtained and no scum was produced in the washing operation or in either of the two rinses following.

Example If The same washing test was made as in Example I, using a detergent mixture consisting of Parts Commercial soap which contained about 22% alkaline builders hence 47 parts pure soap 60 Tetrasodium pyrophosphate 20 Organic sulphonate (sodium salt) made according to the process disclosed in Brandt application Ser. No. 211,946 20 Good detersive action was obtained and no scum developed in the washing operation or in either of two rinses; however, a small quantity of suds appeared during the first rinse.

Example III Parts The same commercial soap used in Example II 60 Tetrasodium pyrophosphate do- Mineral oil sulphonate (sodium salt) made according to the process disclosed in Brandt U. S. Patent No. 2,149,661 percent 25 were mixed and employed as the washing agent in the same manner as in Examples I and II. The results showed good detersive action and no following mixtures:

scum at any time the washing operation or in the rinses.

Example IV Parts Soap 65 Tetrasodium pyrophosphate 20 Mineral oil sulphonate (sodium salt) used in Example III 15 were mixed and used as the detergent in a washing test as followed in the above examples. Although good detersive action was obtained, a small quantity of objectionable scum was produced in the first rinse.

Example V A detergent composed of:

Parts Soap 45 Alkaline soap builder (sodium silicate) 15 Sodium hexametaphosphate 20 Mineral oil sulphonate (sodium salt) used in Example III 20 gave no scum in the wash or in either of the rinses,

Example VI A washing composition including:

Parts Soap 55 Potassium metaphosphate 30 Mineral oil sulphonate (potassium salt) use in Example II 15 caused the formation of no scum in any of the operations. A small amount of suds produced in the first rinse and no scum on either rinse showed that the detersive action andscum-eliminating property continued through the rinses.

Example VII Excellent results as to the prevention of scum in the rinses were obtained by the use of the Parts (a) Soap 45 Tetrasodium-pyrophosphate 35 Mineral oil sulphonate used in Example III 20 (b) Commercial soap used in Example II 60 Sodium hexametaphosphate 32 Mineral oil sulphonate used in Example II 8 While these examples are all directed to a mineral oil sulphonate prepared in a certain manner, it is not to be understood that the invention herein is limited thereto. Other true sulphonates than those given in the examples function in like manner, but have been found to be less desirable from the standpoint of efllciency, scum elimination, and economy. The elimination of scum is marked when the salts of other sulphonic acids are employed, and they generally function in a similar manner to that illustrated by the examples.

Furthermore, salts, other than those set out in the examples, of the three types f compounds forming the essential components of our new washing and deterging composition may be used. For instance, potassium, ammonium, amine and alkylolamine salts of the three compounds may be employed in any combination or mixture, and, as will be understood by those possessing a knowledge of these disclosures, variation of the cations of the compounds will result in compositions of varying properties.

These compositions will be found extremely valuable because of the characteristics disclosed herein for many uses, a few of which may be enumerated as in washing, and emulsifying agents, textile assistants, tanning agents, all cleansing purposes, in uses where goodpenetration is essential as in well-treating fluids, paper making, dyeing, fruit washing, ore concentrating, preparation of plastics, manufacture of inks, coatings, polishes, lacquers, fire-fighting compositions, and many other uses wherein the properties are desirable.

Detergent compositions according to this invention may be prepared in many different forms, such as cakes, powder, beads, flakes, solutions, etc., and may be made into such forms by any of the methods now generally followed for such purposes.

The invention is not limited to the specific uses hereinabove specified or suggested, nor t the physical forms proposed for the compositions, since the characteristics of the detergent compositions contemplated by this invention are retained in any of the forms and their uses are dictated by the demand for such agents of the properties described.

The term sulphonate" as used herein refers to a true sulphonic acid derivative, that is, organic compounds having as a substltuent thereof the radical --SO3 in which the sulphur is joined directly to a carbon atom.

We claim:

1. A detergent composition for cleaning fabrics which dissolves in hard water without substantial formation of curds comprising about 40 t formation of curds comprising about 40 to 60% by weight of a water-soluble soap, about 10 to 40% by weight of a water-soluble salt of a tetraphosphoric acid, and about 40 to 5% by weight of a water-soluble sulphonate obtained by extracting a mineral oil with a selective solvent for the unsaturated constituents,- sulphonating the resulting mineral oil extract while it. is dissolved in liquid sulphur dioxide and neutralizing the sulphonation product.

3. A detergent composition for cleaning fabrics which dissolves in hard water without substantial formation of curds comprising about 40 to 60% by weight of a water-soluble soap, about 10 to 40% by weight of a water-soluble salt of a pyrophosphoric acid, and about 40 to 5% by weight of a water-soluble sulphonate obtained by extracting a mineral oil with a selective solvent for the unsaturated constituents, sulphonating the resulting mineral oil extract while it is.dissolved in liquid sulphur dioxide and neutralizing the sulphonation product.

' 4. A detergent composition for cleaning fabrics which dissolves in hard water without substantial formation of curds comprising about 40 to 60% by weight of a water-soluble soap, about 10 to 40% by weight of a water-soluble salt of a metaphosphoric acid, and about 40 to 5% by weight of a water-soluble sulphonate obtained by extracting a mineral oil with a selective solvent for the unsaturated constituents, sulphonating the resulting mineral oil extract while it is dissolved in liquid sulphur dioxide and neutralizing the sulphonation product.

5. A detergent composition for cleaning fabrics which dissolves in hard water without substantial formation of curds comprising about by weight of a water-soluble sodium soap, about 20% by weight of a. water-soluble sodium salt of pyrophosphoric acid, and about 30% by weight of a water-soluble sulphonate obtained by extracting a mineral'oil with a selective solvent for the unsaturated constituents, sulphonating the resulting mineral oil extract while it is dissolved in liquid sulphur dioxide and neutralizing the sulphonation product.

ROBERT B. COLGATE. EMIL E. DREGER.

CEBHFICATE or oonnscnon. Patent 110. 239L075. August 25, 191 2.

' nosmr B. comm, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, first column, line 6, for the words "it is" read '-it"is a-; line 26, before "modify" insert --may-; and second column, line 50, for "Applications' read --Applicants--; page 2, second column, line 2, for "ammonum" read --smmox'1ium--; page 5, first column, line 11,1,Exsmple I, for

' "No. 2,1Li9,662 --2o" read --No. 2,1h9,662 -50; line 68, Example III,strike out -"do"; and that the said Letters Patent shduld be read with thisporrection therein that the same may conform to the record of the case in the Patent Office.

Signed andsealed this 29th day of September, Ar D. 1914.2

Henry Van Arsdale, (Seal) ActingCom-nfisioner of Patents. 

